Organosilicone having a carboxyl functional group thereon

ABSTRACT

An uncapped polysiloxane composition is provided having the formula: ##STR1## wherein: R is selected from R 2  or --OR 9  wherein R 9  is hydrogen or alkyl; 
     R 1 , which can be the same or different, is selected from R 2 , an amine containing group of the formula --(CH 2 ) n  --F n1  --B n2  --F--NH 2  functional carboxyl group of the general formula: ##STR2## wherein R 5  is hydrogen, alkyl or alkali metal; F is linear or branched alkylene; B is --NR 9 , oxygen or sulfur, wherein R 9  is hydrogen or lower alkyl (C 1-6 ); 
     R 2  can be the same or different and is selected from alkyl, aryl, alkenyl or alkeynyl; 
     R 3  and R 4 , which may be the same or different are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene or alkenyl; 
     a is an integer from 0 to 50,000; and 
     b is an integer from 0 to 100.

RELATED APPLICATION

This application is a continuation in part of copending applicationsSer. No. 420,746 filed Apr. 12, 1995, U.S. Pat. No. 5,596,061.

FIELD OF THE INVENTION

The present invention relates to novel organosilicone compositions and,more particularly, to silicone compositions having a carboxyl functionalgroup thereon.

BACKGROUND OF THE INVENTION

While some carboxyl functional organosilicones are known, they aregenerally difficult and expensive to prepare and the commercial usethereof has therefore been limited. Heretofore, no convenient method fordirectly preparing polysiloxanes containing functional carboxylic acidgroups is known and indirect routes for their preparation have generallybeen used, including hydrosilylation of an unsaturated ester followed byhydrolysis, or alternatively, by hydrolysis of nitrile-containingsilicone fluids. However, polysiloxanes containing one or morefunctional groups such as amino groups are well known and have been usedin a variety of commercial applications but none of such polysiloxanesalso contain functional carboxyl groups. Accordingly, the development ofa method for readily preparing polysiloxanes containing one or morefunctional carboxyl groups would be desirable and it would beparticularly advantageous if such method employed more readily availablematerials such as amino functional polysiloxanes for not only preparingcarboxyl functional polysiloxanes but a variety of organosiliconederivatives thereof as well, including silicone-containing phospholipidcompositions and the like which are readily dispersable or soluble in avariety of solvents, preferably in water.

While, as indicated, certain polysiloxanes containing functionalcarboxylic acid groups and methods for preparing the same haveheretofore been suggested, there is no disclosure or suggestion of thenovel pyrrolidone-containing carboxyl functional silicone compositionsdescribed in copending application Ser. No. 420,746 filed Apr. 12, 1995,now U.S. Pat. No. 5,596,061, of which the present application is acontinuation in part, and the novel pyrrolidone-containing carboxylfunctional silicone compositions of the present invention as well as thenovel method for readily preparing such pyrrolidone-containing carboxylfunctional silicone compositions.

SUMMARY OF THE INVENTION

It is accordingly an object of the present invention to provide novelorganosilicone compositions having at least one pyrrolidone-containingcarboxyl functional group thereon.

It is another object of the present invention to provide a method fordirectly and readily preparing organosilicone compositions having atleast one pyrrolidone-containing carboxyl functional group thereon.

It is a further object of the present invention to provide improvedcosmetic and personal care preparations which include novelcarboxyl-functional silicone-containing compositions and amidoaminederivatives thereof.

It is still a further object of the present invention to provideimproved home care and car care formulations which include novelcarboxyl functional silicone-containing compositions and amidoaminederivatives thereof.

In accordance with the present invention, there has now been discoverednovel polysiloxanes containing one or more carboxylic acid groups and/orthe ester derivatives thereof that may be represented by the followinggeneral formula: ##STR3## wherein:

R₁, which can be the same or different, can be selected from R₂, aprimary amine containing group, and a pyrrolidone containing carboxylfunctional group of the formula: ##STR4## wherein at least one of R₁ isa pyrrolidone containing carboxyl or ester functional group or saltderivative thereof as shown; F, which can be the same or different, islinear or branched alkylene of 1-12 carbon atoms; R₂ is as definedbelow; R₅ can be hydrogen, lower alkyl (C₁₋₆) or alkali metal; n is zeroor 2; n¹ is zero or 1; n² is zero or 1; and B is --NR₉, sulfur (S) oroxygen (O), wherein R₉ is hydrogen or lower alkyl (C₁₋₆), with theproviso that when n is 0 and n² is 1, n' is 1, when n is 2 and n² is 1,n¹ is 0 or 1 and when n is 2 and n² is 0, n¹ is 0;

R₂ can be the same or different and can be selected from alkyl, aryl,alkenyl, or alkynyl;

R₃ and R₄, which may be the same or different, are selected from alkyl,aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene, alkenylor alkynyl;

a can be an integer from 0 to 50,000; and

b can be an integer from 0 to 100.

In another aspect of the present invention there is provided a methodfor preparing polysiloxanes containing one or morepyrrolidone-containing functional carboxylic acid groups and/or theester derivatives thereof, which comprises reacting an organosiliconefluid or composition having at least one primary amine functional groupwith itaconic acid or an ester thereof at an elevated temperature(preferably from about 90° C. to about 130° C.) for a time sufficient toreact, preferably substantially completely react (generally ranging fromabout 1-5 hours), the itaconic and or ester thereof with the functionalprimary amine group(s) on the silicone fluid or composition to form anorganosilicone composition having at least one pyrrolidone-containingcarboxyl functional group.

In yet another aspect of the present invention there is provided analternate method for preparing polysiloxanes containing one or moreester derivatives of carboxylic acid pyrrolidone groups which comprisesreacting an organosilicone fluid or composition having one or morehydride groups (terminal or lateral) on the polysiloxane chain with anN-alkenyl carboalkoxyl group containing a pyrrolidone nucleus portion inthe presence of a noble metal catalyst, preferably soluble platinumcatalyst, at an elevated temperature (preferably between about 65° C.and 130° C.) for the time sufficient to react, preferably substantiallycompletely react, the hydride groups on the silicone fluid orcomposition with the pyrrolidone group.

In a further aspect of the present invention there is provided a novelsilicone-modified amidoamine composition having the formula: ##STR5##wherein:

R₁₀ is the silicone backbone chain as herein described to which at leastone pyrrolidone containing amidoamine derivative of a carboxylfunctional group can be attached as shown;

R₆ is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atomseach, or cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to10 carbon atoms within the oxyalkylene unit;

R₇ and R₈, which may be the same or different, are selected from alkyl,hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl; andpolyoxyalkylene of up to 10 carbon atoms; in addition R₇ and R₈ takentogether with the nitrogen to which they are attached may represent anN-heterocycle.

n is zero or 2;

n¹ is zero or 1;

n² is zero or 1;

n³ is an integer from 2 to 12;

B is --NR₉, sulfur or oxygen, wherein R₉ is hydrogen or lower alkyl(C₁₋₆); with the proviso that when n is 0 and n² is 1, n¹ is 1, when nis 2 and n² is 1, n¹ is 0 or 1, and when n is 2 and n² is 0, n¹ is 0;

F, which may be the same or different is branched or linear alkylene of1-12 carbon atoms; and

d is at least one.

In a still further aspect of the present invention there are providedcosmetic and personal care compositions comprising from about 0.19 toabout 10%, preferably from about 1% by weight of pyrrolidone-containingcarboxyl functional organosilicone compositions and ester and amidoaminederivatives thereof.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention there are provided novelpolysiloxanes comprising a class of carboxyl functional polysiloxaneswhich may be represented by the general formula: ##STR6## wherein:

R₁, which can be the same or different, can be selected from R₂, aprimary amine containing group, preferably of the formula--(CH₂)--F_(n1) --B_(n2) --F--NH₂, and a pyrrolidone containing carboxylfunctional group of the general formula: ##STR7## wherein at least oneR₁ is a pyrrolidone-containing carboxyl or ester functional group orsalt derivative thereof as shown; F, which can be the same or different,is linear or branched alkylene of 1-12 carbon atoms, preferablyethylene, propylene or isobutylene; R₂ is as defined below; R₅ ishydrogen, alkyl, preferably lower alkyl (C₁₋₆), or an alkali metal; n is0 or 2; n¹ is 0 or 1; n² is 0 or 1; and B is --NR₉, sulfur (S) or oxygen(O), wherein R₉ is hydrogen or lower alkyl (C₁₋₆); with the proviso whenn is 0 and n² is 1, n¹ is 1, when n is 2 and n² is 1, n¹ is 0 or 1 andwhen n is 2 and n² is 0, n¹ is 0;

R₂ can be the same or different and can be selected from alkyl, aryl,alkenyl and alkynyl;

R₃ and R₄, which may be the same or are selected from alkyl, aryl,capped or uncapped polyoxyalkylene, alkaryl, aralkylene, alkenyl oralkynyl;

a can be an integer from 0 to 50,000;

b can be an integer from 0 to 100; with the proviso that when a is zero,all R₁ can be the same or different pyrrolidone-containing carboxyl orester functional groups or only the terminal R₁ groups are R₂ groups,and R₃ can be the same or different than the R₂ groups.

It is evident from the general formula above that the polysiloxanecompositions of the present invention have one or morepyrrolidone-containing functional carboxyl or ester group(s) or saltderivative thereof linked terminally, laterally or both terminally andlaterally to the silicone (polysiloxane) chain through a hydrocarbonlinkage which may contain a hetero atom.

The polysiloxane compositions according to the present invention areuseful, for example, as additives for cosmetic and personal careformulations and home and car care products, as well as precursors forsilicone-containing compositions suitable for use in a wide range ofpersonal care and home care products, fiber treating and metal treatingagents and the like which impart such advantages as improved feel,substantivity, reduced surface tension, and anti-stick characteristics.

The novel carboxyl functional polysiloxanes of the present inventionsurprisingly and unexpectedly can be readily and directly prepared bythe reaction of corresponding silicone compositions or fluids having oneor more functional primary amine groups including diamine groupscontaining functional primary amine groups with up to about oneequivalent, preferably about stoichiometric quantities, of itaconic acidor its ester per functional primary amine group(s) at an elevatedtemperature for the time sufficient for substantially all of theitaconic acid or its ester to react with the functional primary aminegroup(s). In general from at least about 0.5, preferably, from about 0.9to about 1.1 equivalents of itaconic acid or its ester per functionalprimary amine group is reacted with the silicone fluid whereinsubstantially all the itaconic acid and preferably all the functionalprimary amine group(s) is reacted and a polysiloxane composition with atleast one pyrrolidone containing functional carboxyl group(s) and/or itsester are formed.

The reaction can be carried out neat or in an inert solvent such asalcohol, hydrocarbon solvent, chlorinated hydrocarbon and the like, asdesired, in general, at elevated temperature up to about 175° C.,preferably from about 90° C. to about 130° C. The reaction readilyproceeds and generally complete reaction of the itaconic acid or itsester with the available functional primary amine group(s) occurs in theMichael Addition Reaction manner with the double bond of the itaconicacid followed by immediate cyclization to form a pyrrolidone group whichwill occur in from about 1 to 5 hours. Routine analytical techniques foramine and acid values as well as monitoring water and/or alcoholevolution being used to determine completion of the reaction.

Primary amine functional silicone fluids suitable for use in accordancewith the practice of the invention, having one or more primary aminefunctional group(s), including diamine group(s) that contain a primaryamine group (s), which may be linked terminally, laterally or bothterminally and laterally, as desired, are well known and are availablecommercially, for example, from Dow Corning, Th. Goldschmidt AG andShin-Etsu. While the equivalent weight of the silicone fluids orcompositions which may be employed in the preparation of thepolysiloxanes of the present invention is not critical, and suitablecompositions may have equivalent weights of 5,000 to 10,000 or evenhigher, silicone fluids having equivalent weights from about 500 toabout 5,000 are in general preferred.

As indicated, the polysiloxane compositions of the present invention arereadily prepared by reaction of primary amine functional silicone fluidswith itaconic acid or its ester. Itaconic acid (methylene succinic acid)is a compound of the formula:

    CH.sub.2 ═C (COOR.sub.9) CH.sub.2 COOR.sub.9

wherein

R₉, which can be the same or different, is hydrogen or lower alkyl (1-6carbon atoms).

The compound itaconic acid is available commercially from Rhone Pouleucand Pfizer Chemicals Division whereas ester derivatives thereof areavailable from Morflex Inc., Greensboro, N.C. The compounds are producedby known fermentation techniques although chemical synthesis methods arealso known.

The novel carboxyl-functional polysiloxanes, or ester derivativesthereof, of the present invention can also be readily prepared by ahydrosilylation reaction wherein a silicone fluid or composition havingone or more hydride substituents on the silicone chain (terminal,lateral or combination or terminal and lateral) is added to a N-alkenylcarboalkoxy containing a pyrrolidone nucleus in the presence of a noblemetal (Group VIII metal) catalyst, preferably soluble platinum, at anelevated temperature (65° C. to 130° C.) for a time sufficient forsubstantially all of the N-alkenyl carboalkoxy containing pyrrolidone toreact with the hydride group(s). The N-alkenyl carboalkoxy containingpyrrolidone reactant can have a N-allyl or higher olefinic group of 3 ormore carbon atoms which can also include at least one hetero atom. Thereaction can be carried out neat or in inert solvents such as toluene,benzene, chlorobenzene, heptane and the like. In general, from about 0.5up to about one equivalent, preferably from about 0.9 to about 1.1equivalents of the N-alkenyl pyrrolidone groups per functional hydridegroups is reacted with the silicone fluid wherein substantially all theN-alkenyl carboalkxy containing pyrrolidone and, preferably all of thefunctional hydride groups are reacted. Suitable platinum catalystsinclude solubilized platinum or platinum metal on inert supports such asalumina, charcoal and the like. In general from about 10⁻³ to 10⁻⁶ molesof platinum per mole of hydride group can be used.

In another aspect of the present invention, there are provided novelsilicone-containing amidoamines suitable for use as surfactants and avariety of other applications which are preferably derivatives of thenovel carboxyl-functional polysiloxane compositions of the invention ashereinabove described. The novel amidoamine compositions of theinvention may be represented by the general formula: ##STR8## wherein:R₁₀ is a silicone backbone chain as herein described to which at leastone pyrrolidone-containing carboxyl functional group or amidoaminederivative thereof is attached as hereinabove shown;

R₆ is hydrogen or alkyl, hydroxyalkyl or alkenyl up to 6 carbon atomseach, cycloalkyl of up to 6 carbon atoms or polyoxyalkylene of up to 10carbon atoms, preferably from 2 to 5 carbon atoms, within theoxyalkylene unit and at least one R₆ is hydrogen;

R₇ and R₈, which may be the same or different, are selected from alkyl,hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl, andpolyoxyalkylene of up to 10 carbon atoms; in addition R₇ and R₈ takentogether with the nitrogen to which they are attached may representN-heterocycle.

F, which can be the same or different, is linear or branched alkylene of1-12 carbon atoms;

B is --NR₉, sulfur or oxygen, wherein R₉ is hydrogen or lower alkyl(C₁₋₆); with the proviso that when n is 0 and n² is 1, n¹ is 1, when nis 2 and n² is 1, n¹ is 0 or 1, and when n is 2 and n² is 0, n¹ is 0;

n is 0 or 2;

n¹ is zero or 1;

n² is zero or 1;

n³ is an integer from 2 to 12;

d is an integer from 1 or greater, generally from 1-50 and preferably2-10.

The novel silicone-containing amidoamine compositions of the inventioncan be prepared as follows: ##STR9## wherein: R₁₀ is a silicone backbonechain as herein described to which at least one pyrrolidone-containingcarboxyl functional group or amidoamine derivative thereof is attachedas hereinabove shown;

R₅ is hydrogen, lower alkyl (C₁₋₆) or alkali metal;

R₆ is hydrogen or alkyl, hydroxyalkyl or alkenyl up to 6 carbon atomseach, cycloalkyl of up to 6 carbon atoms or polyoxyalkylene of up to 10carbon atoms, preferably from 2 to 5 carbon atoms, within theoxyalkylene unit and at least one R₆ is hydrogen;

R₇ and R₈, which may be the same or different, are selected from alkyl,hydroxyalkyl, carboxyalkyl of up to 6 carbon atoms in each alkyl, andpolyoxyalkylene of up to 10 carbon atoms; in addition R₇ and R₈ takentogether with the nitrogen to which they are attached may represent anN-heterocycle.

F, which can be the same or different, is linear or branched alkylene of1-12 carbon atoms;

B is --NR₉, sulfur or oxygen, wherein R₉ is hydrogen or lower alkyl;with the proviso that when n is 0 and n² is 1, n¹ is 1, when n is 2 andn² is 1, n¹ is 0 or 1, and when n is 2 and n² is 0, n¹ is 0;

n is 0 or 2;

n¹ is zero or 1;

n² is zero or 1;

n⁴ is an integer from 2 to 12;

d and D is an integer from 1 or greater, generally from 1-50 andpreferably 2-10. The reactant ratio of the amine reactant to thecarboxyl reactant on the silicon is preferably 1:1 but can be varied inratio from 1:0.8 to 1:1.2.

The above coupling reaction for preparing the silicone-containingamidoamine compositions can be carried out neat or can be carried out inan inert solvent such as xylene, toluene, chlorobenzene or the like.While the equivalent weight of the silicone-containing amidoaminecompositions is not critical, preferably the equivalent weight of suchcompositions are from about 500 to 1500.

The novel pyrrolidone-containing functional carboxyl polysiloxanecompositions of the invention and amidoamine derivatives thereof displaymany of the well known properties of silicone fluids such as emolliency,emulsification, anti-stick, smoothing, substantivity, lubricating andsurfactancy properties. Thus, such compositions can be readilyincorporated into a variety of products such as personal care and homecare formulations as well as many other compositions that providelong-lasting effects on various substrates such as skin, hair, naturaland synthetic fibers (textiles), plastics, metals, paper and the like.In addition, the novel carboxyl-functional polysiloxane compositions andamidoamine derivatives thereof are suitable reactants in combinationwith, for example, a variety of phosphate ester and polyphosphate esterhalide and the like reactants for the ready preparation oforganosiloxane compositions such as silicone-containing phospholipidcompositions which have water soluble and water dispersibilitycharacteristics and exhibit a wide range of beneficial properties.

It is therefore a further aspect of the invention to use the novelcompositions of the invention, for example, in cosmetic and the likepersonal care preparations, especially for skin treatment and hair care;car and home care products, especially for metal and floor surfacecleaning and protection, and the like.

In this connection, personal care formulations can be skin-treatmentcremes and lotions, hair conditioners and after-bath skin moisturizers,depending on whether the emphasis is on the conditioning effect or onthe cleaning effect including the effect on better combability in haircare products. Other formulations where the unique properties of thenovel compositions of the invention can be utilized include make-upcremes, sunscreens, lipstick, pressed powders, skin-toners, deodorants,antiperspirants and the like. Personal care preparations to which thenovel polysiloxane compositions of the invention have been added inamounts of 0.1 to 10 weight percent, and which can contain otheradditives including other silicone fluids, provide skin treatingproducts with non-irritating, non-greasy film on the skin that does notevaporate and therefore provides long lasting protection. In hair careproducts, such as, hair tonics or hair sprays, the composition of theinvention in amounts of 0.1 to 5% or 10% bring about a significantimprovement in combability of the hair as well as development offullness and gloss.

Conventional additives, such as thickeners, perfumes, presevatives,complexing agents, opacifiers, luster development agents and the likemay be added to the personal and hair care products.

In addition, the novel polysiloxane compositions of the inventiondemonstrate useful metal and floor surface cleansing and protectionproperties when incorporated into home and car care products. As acomponent of floor and car surface wax products in an amount of from 1%to 10%, they form a non-greasy glossy film on the surface which does notevaporate and is resistant to weather and cleansing agents, thereforeproviding long lasting protection.

Among other advantages of the novel polysiloxane compositions of theinvention are their usefulness as paper and textile sizing andlubricating agents; treating agents for fillers, paper and plastics;coatings for glass, plastics and minerals; anticorrosion agents formetal products; adhesion promoters for metal primers and paints and thelike.

The preparation of specific compositions of the invention is illustratedby the following specific examples which are provided herein forpurposes of illustration only and are not intended to limit the scopetherein.

EXAMPLE 1

An alpha-omega diamino functional polysiloxane fluid obtainedcommercially under the designation Tegomer A-Si2120 from GoldschmidtCompany is used in this example. The amine content of the fluid is 3.5%which corresponds to a molecular weight of 914.

91.4 grams of the above polysiloxane fluid (0.1 moles) is admixed with26 grams (0.2 moles) of Itaconic Acid in a reaction vessel. Uponcombination of the reactants, a heterogeneous mixture is formed.External heat is applied to the reaction vessel bringing the reactionmixture to a temperature of about 110° C., whereupon the reactionmixture becomes completely homogeneous while the temperature rises to140° C.

After a heating period of 4 hours, a total of 7.5 ml of volatiles arecollected. The acid value of the reaction mixture is 81.6 (theoretical95.5) while the alkali number is nil, thus confirming that there is thepresence of carboxyl groups on the product.

EXAMPLE 2

An alpha, omega-Bis primary amino alkyl dimethyl polysiloxane fluid withan average molecular weight about 1579.5 and having the general formula:##STR10## obtained commercially from Shin-Etsu under the designationX-22161A is used in this example.

A mixture of 994.5 grams of the above polysiloxane fluid (0.6296 moles)and 163.7 grams (1.25 moles) of Itaconic Acid is formed in a reactionvessel and heated (slowly to about 90° C. at which point an exothermoccurs raising the reaction vessel temperature to 130° C. and waterstarts to evolve.

The reaction mixture is heated to and maintained at a temperature of140° C. to 150° C. for a period of 3 hours during which time about 20ml. of water and other volatiles are collected. A clear, yellow viscousliquid is formed having an alkali number of 0.

The mixture is then cooled to 90° C. and 192.6 grams (an excess) ofdimethylaminopropylamine is admixed therewith. The temperature in thereaction vessel is increased to 170° C. to 185° C. and maintained atthat temperature for an 4 additional hours during which time a total of92 ml. of volatiles is collected.

The reaction mixture is then cooled to about 50° C. and subjected to avacuum of 30 mm. While the vacuum is slowly drawn to 3 mm, the reactionvessel temperature is increased from 75° C. to 15° C. The productresidue collected from the reaction vessel has a 92% yield with analkali number of 67 (theoretical alkali number is 57).

200.88 grams of the reaction product above (0.12 moles) is then admixedwith 75.4 grams of 40% active phosphate ester halide reactant and a 2:1mixture of propylene glycol and water to obtain a solution having 30%solids. The phosphate ester halide reactant used is prepared by thereaction of 3 moles of epichlorohydrin and one mole of sodium dihydrogenphosphate.

The reaction admixture is heated for 4 hours at a temperature range of75° C. to 85° C. whereupon a homogeneous, clear liquid solution isobtained having a NaCl content of 1.8% (theoretical NaCl is 1.86%).

The product formed when mixed with water produced a great deal of stablefoam whereas the polysiloxane functional amino fluid used as a startingmaterial in the example provided no foam when mixed with water.

EXAMPLE 3

Another sample of a diamino polysiloxane fluid such as used in example 2is used in this example. The average molecular weight of the sample is1729 which corresponds to a percent amine of 1.85%.

To 43.2 grams (0.025 moles) of the above siloxane fluid in a reactionvessel is added with mixing 6.5 grams (0.05 moles) of Itaconic acid. Themixture is heated to 90° C. whereupon an exotherm occurs raising thetemperature to 130° C. and resulting in a liquified viscous yellow mass.The reaction mixture is heated to and maintained at a temperature of135°-140° C. for 3 hours while some volatiles are collected and at whichpoint the alkali number is zero.

There is then added to the reaction mixture 7.7 grams (0.075 moles, 50%excess) of dimethylamino propylamine (DMAPA) and the temperature israised to 165° C. where it is held for four additional hours. Thereaction mixture is subjected to vacuum stripping to remove excess DMAPAat a reaction vessel temperature of 125° C. and a vacuum of 10 mm. Thealkali number of the reaction product residue is 54 (theoretical 52.9).

A combination of 21.2 grams (0.01 moles) of the reaction product above,6.25 grams (0.0061 mole) of 40% active phosphate ester halide reactantprepared as in example 2, 16 grams of isopropanol and 16 grams of waterhaving a solid content of 40% is prepared in a reaction vessel. Thecombined reactants are heated to a temperature of 95° C. for four-fivehours at which time a clear yellow solution is obtained having a NaClcontent of 2.4% (theoretical 1.9%).

The product formed when added to water produces a great deal of stablefoam.

EXAMPLE 4

A lateral (pendant) amino functional silicone fluid having an averagemolecular weight of about 3720 obtained from Shin-Etsu under the productdesignation KE-864 is used in this example.

A mixture of 377 grams (0.1013 moles) of the silicone fluid and 13.2grams (0.1013 moles) of Itaconic acid is formed in a reaction vessel andheated to a temperature of 160° C. for about two hours.

A clear melt is formed having an acid number of 11.6 (theoretical 14.6).

EXAMPLE 5

A pendant (lateral) amino functional silicone fluid having an averagemolecular weight of 4400 obtained from Shin-Etsu under the productdesignation KF865 is used in this example.

88 grams (0.02 moles) of the silicone fluid is admixed with 2.6 grams ofItaconic acid (0.02 moles) and heated to a temperature of 130°-140° C.whereupon a clear melt is obtained and then continued heating for anadditional two hours.

After heating for two hours, the reaction mixture is cooled to 70° C.and 4.08 grams (an excess) of dimethylaminopropylamine (DMAPA) isadmixed therewith. The reaction mixture is then heated to a temperatureof 165° C. for four hours, cooled to 70° C. and vacuum stripped at 30-10mm for three hours while slowly raising the temperature to 110° C.

The reaction product residue is a clear liquid having an alkali numberof 12.3 (theoretical 12.2) and an acid number of 0. i.r. analysisconfirms the presence of an amide linkage.

EXAMPLE 6

A pendant (lateral) amino functional silicone fluid obtained fromShin-Etsu under the product designation KF 865 is used in this example.The silicone fluid has an amine value of 0.2219 percent whichcorresponds to an amine equivalent weight of 5675.

665.9 grams (0.1173 equiv. wt.) of the silicone fluid and 15.25 grams ofItaconic acid (0.1173 mole) are combined with 150 ml of xylene in areaction vessel and heated to a temperature of 130°-140° C. underreflux. After heating for 4 to 5 hours under reflux, 2.3 ml of water isremoved (theory 2.1).

17.9 grams of dimethylaminopropylamine (DMAPA) is then admixed with thereaction mixture and heated under reflux at a temperature of 160°-170°C. for a period of about 4 hours during which time an additional 2.1grams of water is removed. The reaction mixture is cooled to about 70°C. and vacuum stripped at 30-40 mm to remove low boiling volatiles. Avacuum of 5-10 mm is then applied to the reaction mixture and thereaction vessel is heated for three hours at 140° C. The reactionproduct is a clear liquid having an alkali number of 9 (theoretical9.55) which corresponds to an amine equivalent weight of 6233.

EXAMPLE 7

This example illustrates an alternate procedure of preparing apolysiloxane composition having at least one pyrrolidone containingcarboxyl functional group(s).

A mixture of 122.4 grams of octamethyl-cyclotetrasiloxane, 13.4 grams oftetramethyldisiloxane, 0.7 grams of activated charcoal and 0.07 gramsconcentrated sulfuric acid are charged into a reaction vessel and heatedwith agitation to 65° C. for 24 hours. The mixture is filtered and thefiltrate is subjected to reduced pressure at 70° C. for 48 hours. Acolorless liquid is obtained having a number average molecular weight ofabout 1580 which is terminated in silicon hydride as determined by NMR.

A solution of 15.8 grams (0.1 mole) of dimethyl itaconate in 30 ml ofmethanol is added at ambient to a reaction vessel containing a solutionof 5.7 grams (0.1 mole) alylamine in 10 ml methanol. Upon completeaddition of the dimethyl itaconate, a mild exotherm is produced raisingthe reaction mixture temperature to 55° C. Following this, the reactionmixture is held at reflux for 3 hours. The reaction mixture is strippedof solvent and the product (N-allyl 4 carbonmethoxy pyrrolidone) isisolated by distillation of 115° C. A colorless liquid is obtained in85% yield.

158 grams of the silicone hydride terminated polysiloxane materialprepared above is charged to a reaction vessel and 1 ml of a 0.1Nchloroplatinic acid solution in tetrahydrofurane (THF) is added thereto.The reaction mixture is heated to 90°-95° C., the heat source is removedand 36.6 grams (0.2 Equivalents) of the itaconate/allylamine reactionproduct prepared above is added to the reaction vessel. After a briefinduction period, the temperature of the mixture starts to rise slowlyand the reaction temperature is controlled between 110°-115° C. by therate of addition. Following complete addition of the pyrrolidonereaction product, the reaction mixture is heated at 120° C. for 3 hours.

Analysis of the reaction product indicates complete absence ofSilicone-Hydride absorption and allylic unsaturated is also absent. NMRanalysis confirms that the resulting reaction product is an alpha-Omegacapped carbomethoxy pyrrolidone containing silicone fluid.

EXAMPLE 8

Skin care creme compositions are prepared having the followingproportion of ingredients. The pyrrolidone-containing carboxylfunctional polysiloxane composition (PCA) and amidoamine derivativethereof (PDM) of Example 5 are used in this example.

    ______________________________________                                                                  SAMPLE   SAMPLE                                                               A        B                                                                    % BY     % BY                                       PART  RAW MATERIAL        WT.      WT.                                        ______________________________________                                        A     Cetyl Phosphate (Monafax 160)                                                                     0.5      0.5                                        A     Potassium Hydroxide (45% in H.sub.2 O)                                                            0.2      0.2                                        A     Deionized Water     77.78    77.79                                      A     Lactic Acid (88% in H.sub.2 O) to pH 6.0                                                          0.02     0.01                                       A     Glycerine           10.0     10.0                                       B     Propylene Glycol Stearate                                                                         5.0      4.0                                        B     Cetyl Alcohol       2.0      2.0                                        B     Glyceryl Monostearate                                                                             3.0      3.0                                        B     Example 5 PCA                1.5                                        B     Example 5 PDM       1.5                                                 ______________________________________                                    

Heat Parts A and B individually to 75° C. with stirring. Add Part Bslowly to Part A with stirring. Cool with mixing to 30° C.

Both formulations yield smooth glossy cremes which spread easily, breakquickly and impart a smooth non-greasy emmolliency to the skin. In eachcase, the smooth afterfeel on the skin persists even after exposure towater suggesting utilization of these silicone compositions inwater-resistant skin-protection cremes, suntan products and make-up.

EXAMPLE 9

The pyrrolidone-containing carboxyl functional silicone composition(PCA) and amidoamine derivative thereof (PDM) of Example 6 is used inthis example. Hair conditioning spray/dip formulations are preparedhaving the following proportion of ingredients.

    ______________________________________                                                                  Sample   Sample                                                               A        B                                                                    % by     % by                                       PART  RAW MATERIAL        Wt.      Wt.                                        ______________________________________                                        A     Glycerine           2.0      2.0                                        A     Deionized Water     87.45    87.45                                      A     Citric Acid         0.05     0.05                                       B     Milk Lipid Phospholipid                                                                           2.0      2.0                                        B     Amine Oxide Lipid   2.5      2.5                                        B     Cetyl/stearyl Alcohol                                                                             2.0      2.0                                        B     Refined Milk Triglyceride                                                                         3.0      3.0                                        B     Example 6 PCA       --       1.0                                        B     Example 6 PDM       1.0                                                 ______________________________________                                    

Heat Parts A and B individually to 75° C. with stirring. Add Part A toPart B slowly with stirring. Cool with mixing to 30° C. The formulaeyield a fine mist when used in a hand-pumped aerosol dispenser.

A hair swatch dipped in the test samples and dried, exhibit curlretention, good wet-and-dry combing properties, a silkier texture andbetter residual gloss versus a water-treated swatch indicating thesuitability of the silicone compositions as an additive in hairgrooming/conditioning products.

EXAMPLE 10

Liquid car care wax formulations are prepared having the followingproportion of ingredients by weight. The pyrrolidone-containing carboxylfunctional polysiloxane composition (PCA) and amidoamine derivativecomposition thereof (PDM) of Example 6 are used in this example.

    ______________________________________                                              RAW                                                                     PART  MARTERIAL    SAMPLE A  SAMPLE B                                                                              SAMPLE C                                 ______________________________________                                        A     Example 6 PCA          4.5                                                    Example 6 PDM          4.5                                                    DC 200 Fluid 2.0       2.0     2.0                                            (10,000 cs)                                                                   Carnauba #1  6.0       6.0     6.0                                            Yellow                                                                        Acintol FA-2 3.0       3.0     3.0                                            Isopar H     22.0      22.0    22.0                                     B     Water        53.0      53.0    53.0                                           Kapolite SF  7.0       7.0     7.0                                            TEA          0.5       0.5     0.5                                      C     Isopar H     2.0       --      --                                             GE 1705      3.0       --      --                                             GE 1706      1.5       --      --                                       Coefficient of Friction                                                                      0.0963    0.0963    0.0963                                     ______________________________________                                    

Lubricity and glide evaluation tests using a 50 gram brass weight andinclined plane adjustable angle device is used to determine thecoefficient of friction of wax treated "E" Coat Panels. The abovecoefficient results show that all the silicone containing waxformulations including control wax Sample A have good lubricity andglide compared to a control panel with no wax coating having acoefficient of friction of 0.4663.

Control Wax Sample A is compared to Sample B and Sample C formulationstogether with four commercial automobile wax products by evaluation forgeneral appearance after application, gloss and shine and durabilitytesting. The treated panels are evaluated for water beading by using awater spray. After initial water bead testing, the panels are placedinto an automatic dishwasher and washed with a harsh commercialdetergent to simulate automatic car washing. The tests show that SampleB is more durable to harsh detergent than the control siliconecontaining formulation (Sample A) and three of the four differentcommercial products. The above formulations are reapplied to metal testpanels and further testing is conducted using repeated automaticdishwashing cycles. After a series of ten dishwashing cycles all testpanels produce a water bead indicating that the panel are still coatedwith wax.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that within the scope of theappended claims, the invention may be practiced otherwise than asspecifically described and illustrated.

What is claimed is:
 1. A personal care and cosmetic compositioncomprising at least 0.1% of a polysiloxane composition having theformula ##STR11## wherein: R₁, which can be the same or different, isselected from R₂, an amine containing group of the formula--(CH₂)--F_(n1) --B_(n2) --F--NH₂ or a pyrrolidone-containing functionalcarboxyl group of the general formula: ##STR12## wherein at least one R₁is a pyrrolidone containing functional carboxyl group or esterderivative thereof as shown; R₂ is as defined below; R₅ is hydrogen,lower alkyl (C₁₋₆) or alkali metal; F which can be the same ordifferent, is linear or branched alkylene of 1-12 carbon atoms; B is--NR₉, oxygen or sulfur wherein R₉ is hydrogen or lower alkyl (C₁₋₆) ; nis zero or 2; n¹ is zero or 1, an n² is zero or 1 with the proviso thatwhen n is zero and n² is 1, n¹ is 1, when n is 2 and n² is 1, n¹ is zeroor 1 and when n is 2 and n² is zero, n¹ is zero.
 2. The polysiloxanecomposition as claimed in claim 1, wherein R₅ is hydrogen or loweralkyl.
 3. The polysiloxane composition as claimed in claim 1, wherein R₁is R₂ or a pyrrolidone-containing carboxyl functional group or esterderivative thereof and at least one of R₁ is a pyrrolidone-containingcarboxyl functional group or ester derivative thereof.
 4. Thepolysiloxane composition as claimed in claim 1, wherein at least oneterminally linked R₁ group is a pyrrolidone containing carboxylfunctional group or ester derivative thereof.
 5. The polysiloxanecomposition as claimed in claim 1, wherein R₃ and R₄ are methyl and a isat least
 1. 6. The polysiloxane composition as claimed in claim 1,wherein both terminal R₁ groups are R₂ and a and b are each at least 1.7. The polysiloxane composition is claimed in claim 1, wherein when a iszero, all the R₁ groups are the same.
 8. The polysiloxane composition asclaimed in claim 1, wherein when a is zero, the R₃ groups can be thesame or different than the R₂ groups.
 9. The polysiloxane composition asclaimed in claim 1, wherein whela is zero, the R₃ groups are the same asthe R₂ groups.
 10. A car care wax formulation comprising at least 1% ofa polysiloxane composition having the formula ##STR13## wherein: R₁,which can be the same or different, is selected from R₂, an aminecontaining group of the formula --(CH₂)--F_(n1) --B_(n2) --F--NH₂ or apyrrolidone-containing functional carboxyl group of the general formula:##STR14## wherein at least one R₁ is a pyrrolidone containing functionalcarboxyl group or ester derivative thereof as shown; R₂ is as definedbelow; R₅ is hydrogen, lower alkyl (C₁₋₆) or alkali metal; F which canbe the same or different, is linear or branched alkylene of 1-12 carbonatoms; B is --NR₉, oxygen or sulfur wherein R₉ is hydrogen or loweralkyl (C₁₋₆); n is zero or 2; n¹ is zero or 1, an n² is zero or 1 withthe proviso that when n is zero and n² is 1, n¹ is 1, when n is 2 and n²is 1, n¹ is zero or 1 and when n is 2 and n² is zero, n¹ is zero,R₂ canbe the same or different and is selected from alkyl, aryl, alkenyl oralkynyl, R₃ and R₄, which may be the same or different are selected fromalkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene,alkenyl or alkynyl; a is an integer from 0 to 50,000; and b is aninteger from 0 to 100; with the proviso that when a is zero, all R₁ canbe the same or different pyrrolidone-containing carboxyl or esterfunctional groups or only the terminal R₁ groups are R₂ groups, and R₃can be the same or different than the R₂ groups.